Chapter 1

Thermomechanical Treatments for Ni-Ti Alloys

F.M. Braz Fernandes, K.K. Mahesh and Andersan dos Santos Paula
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/56087

1. Introduction
Thermomechanical treatments for shape memory alloys (SMA) are found to be one of the
more economical, simpler, and efficient methods adopted for manipulating the
transformation properties. The stability of phase transformation has been found to depend
upon the thermomechanical treatments, such as hot- or cold-working, heat-treatment and
thermal cycling. It has perhaps more important and wide reaching ramifications than many
of the other stages in the fabrication of components and structures.
During the stages of preparation of SMA, hot working is adopted as one of processes in the
form of rolling or drawing to incorporate the shape memory effect (SME). Such alloys can be
directly employed for the applications. However, most of the times, the ingots are finally cold
worked in the form of rolling or drawing before delivering to the application purpose. This
allows the application engineers to subject the alloys to appropriate thermal/mechanical
treatment in order to obtain the SMA with desired phase transformation properties. Hence,
a sequence of cold work followed by heat treatment is considered to be a productive method
to tailor the SME and superelasticity (SE).
In order to emphasize the various methods of thermal, mechanical, and thermomechanical
treatments, the Chapter is divided into the following Sections and Sub-sections.
i.
ii.
iii.
iv.
v.
vi.

Cold working
Cold working followed by heat treatments
Effect of cooling rate during heat treatments
Hot working
Thermal cycling
Severe plastic deformation
a. High-pressure torsion (HPT)
b. Equal channel angular pressing (ECAP)
vii. Concluding remarks
2013 Braz Fernandes et al., licensee InTech. This is an open access chapter distributed under the terms of
the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

4 Shape Memory Alloys Processing, Characterization and Applications

2. Cold working
Cold working can induce dislocations and vacancies in the Nickel-Titanium (Ni-Ti) alloys. It
is suggested that the possible mechanisms for the martensite stabilization in the Equiatomic
Ni-Ti alloys come from deformed structures and deformation induced dislocations/
vacancies. Thermomechanical treatments of Ni-Ti SMA are important for the optimization
of the mechanical properties and phase transformation characteristics. An important
characteristic in the Ni-Ti SMA is the stability on direct and reverse transformations, related
to the sequence and transformation temperatures, and thermal hysteresis [1-5]. The
transformation temperatures in Ni-Ti SMA have been shown to be related to the presence of
lattice defects introduced by cold working [6, 7]. Wu et al., (1996) showed that the defects
induced during cold working have the effect of suppressing the martensitic transformation
and promoting the R-phase transformation [8]. The residual internal stress induced by coldworking defects is considered to be responsible for the R-phase transformation [9]. The
deformation mechanisms and morphologies in polycrystalline martensitic CuZnA1 alloy
have been examined by Adachi and Perkins [10]. They observed that a variety of
deformation morphologies, including variant-variant coalesce, stress-induced martensite to
martensite transformation, injection of foreign variants to plate groups, and internal
twinning and slip, are all exhibited simultaneously in moderately cold-worked specimens.
Ni-Ti alloys have a wider application in the form of wires. Therefore, an understanding of
the wire drawing properties is important. Thin oxide film with a smooth surface on TiNi
wires can be used as a lubricant during the drawing process. However, thick oxide films
which have cracks and spalling on the surface can be detrimental to the drawing surface and
depress the shape memory effect and pseudoelasticity of TiNi SMA. MoS2 is an effective
lubricant for wire drawing of TiNi SMA [8]. Also, cold rolling has been one of the widely
adopted processing techniques in order to obtain Ni-Ti alloy in the sheet form. In a study of
the cold-rolled equiatomic TiNi alloy, it was found that the same phenomena of martensite
stabilization appear, as reported in Cu-based shape memory alloys [9, 10]. It is well known
that the martensite in the Ti50Ni50 alloy has 24 variants [11]. The variants will accommodate
each other under thermal or mechanical stress. It is reasonable to suggest that the stress
exerted by cold rolling causes the variants to accommodate, i.e., the stress forces the
preferred orientated variants to accommodate the deformation strain in the favorable stress
direction. An intensive study of the microstructure of the deformed martensite shows, in
addition to the deformed martensite plates, a large number of dislocations and vacancies
can also be induced during the cold rolling. These deformation-induced dislocations and
vacancies have an important effect on the martensitic stabilization [9].
In Fig. 1, DSC thermograms of the Ni-Ti alloy plate subjected to 40% cold working are
shown. When the cold worked specimen is heated from RT up to around 300C, no phase
transformation is observed and on the further heating, a broad upward peak appears
around 350C corresponding to recrystalization process. However, on cooling to RT, a clear
exothermic peak appears around 75C and that is attributed to AM phase transformation.
While heating again from RT, the DSC thermogram shows an endothermic peak around

Thermomechanical Treatments for Ni-Ti Alloys 5

85 C corresponding to MA phase transformation and while cooling the reverse phase

transformation, AM, is observed.

Figure 1. DSC thermograms of the Ni-Ti SMA plate initially cold worked up to 40% and heated to
500C (in blue), and after (in red).

In Fig. 2, 3-d representation of the XRD profiles obtained at different temperatures from RT
to 400C for the 40% cold worked Ni-Ti specimen is shown. XRD spectra obtained at RT
show the peaks corresponding to B19 structure, which are broad and with low intensity. As
the temperature is increased, the peak corresponding to B2 structure starts to emerge
around 190 C and on further heating, the intensity of the peak increases. Broad and low
intensity peaks are due to the deformation induced dislocations and vacancies which
suppresses the martensitic transformation [12-14].

6 Shape Memory Alloys Processing, Characterization and Applications

Figure 2. 3-d representation of the XRD profiles obtained at different temperatures from RT to 400C
for the 40% cold worked Ni-Ti specimen.

3. Cold working followed by heat treatments

Heat treatment for metals and alloys has been proved to be an effective and economical
process in order to maneuver their properties. Various factors, such as the HTT, annealing
time and cooling rate after annealing have their own effects on the final state of the
metal/alloy. In the above sub-section, it is mentioned that the defects induced during cold
working have the effect of suppressing the martensitic transformation [8]. On the contrary,
there is a possibility that a reverse phenomenon (restoration) would occur in a rather
enhanced manner upon annealing through thermal activation processes of point defects.
The migration of vacancies and interstitials could facilitate promotion of the martensitic
transformation [15]. In this sub-section, the dependence of heat-treatment on the
composition and thermal/mechanical history of the alloys has been explained. Heattreatment plays a crucial role in fixing Ms. The detection of R-phase is found to be critical
with the positioning of Ms in relation to Rs. If Ms is above Rs, R-phase is found to be masked
by the martensite phase. Earlier, from electrical resistivity measurements, it was shown that
while cooling from austenite phase, if R-phase exists, it preceded the martensite phase and it
was regarded as the pre-martensitic phase [16]. However, later it was shown that both
phases coexist at the same temperature, and it has been confirmed by the DSC study on the

Thermomechanical Treatments for Ni-Ti Alloys 7

phase transformation in the 40% cold worked, near equi-atomic NiTi alloy subjected to
water quenching from 400C [17].
Phase transformations associated with SME in Ni-Ti alloys can be one-stage, B19I B2, twostage including an intermediate R-phase stage, or multiple-stage depending on the thermal
and/or mechanical history of the alloy. In a recent report, it has been highlighted the effect of
(i) deformation by cold-rolling (from 10% to 40% thickness reduction) and (ii) final
annealing on the transformation characteristics of a Ti-rich NiTi shape memory alloy. For
this purpose, one set of samples initially heat treated at 500 C followed by cold-rolling (10
40% thickness reduction) has been further heat treated at various temperatures between 400
and 800 C. Phase transformations were studied using differential scanning calorimetry,
electrical resistivity measurements and in situ X-ray diffraction. A specific pattern of
transformation sequences is found as a result of combination of the competing effects due to
mechanical-working and annealing [18].
Fig. 3 (a & b) show the Differential Scanning Calorimeter (DSC) and Electrical Resistivity
(ER) curves for (i) as-received (AR), (ii) annealed at 500C (HT500) and (iii) annealed at
500 C/cold-rolled to 30%/annealed at 500C (TMTCR30HT500) samples. For the AR sample,
both in the case of DSC & ER techniques, multiple-step (B2R, B2B19, RB19, while
heating and cooling) phase transformations are observed. For the HT500 sample, in both

Figure 3. (a) DSC and (b) ER curves for AR, HT500 and TMTCR30HT500 samples

8 Shape Memory Alloys Processing, Characterization and Applications

techniques, during heating and cooling, one-step (B19B2) phase transformation is found
to be present. Further, in the case of TMTCR30HT500 sample, one-step (B19B2) phase
transformation is detected. During heating (for AR samples), a small kink in the DSC and a
small hump in ER plots around 60 C show the presence of R-phase associated to multiplestep, (B19R, B19B2, RB2), phase transformation.
The effects of various heat treatment temperatures (HTT) on samples after being cold-rolled
to different extents (10 to 40% thickness reduction) are presented in Fig. 4. All the samples
were annealed at 500 C before cold-rolling. Figs. 4 (a to d) show the transformation
temperatures (Af, As, Rfh, Rsh, Rsc, Rfc, Ms and Mf, obtained from DSC thermograms) as a
function of HTT, for the samples annealed after being cold worked up to 10%, 20%, 30% and
40%, respectively. A, R and M are the austenite, rhombohedral, and martensite
phases; suffixes s and f are the start (1%) and finish (99%) transformation temperatures;
and c and h refer to cooling and heating, respectively.
140

(b)

100

Af
As

80

Ms
Mf

60

40

400

500

600

700

800

Transformation Temperature (C)

Transformation Temperature (C)

(a)
120

120

Af
As
Rfh

80

Rsh
Rsc
Rfc

40

Ms
Mf

900

400

Heat Treatment Temperature (C)

80

Af
60

As
Rsc
Rfc

40

Ms
Mf

20

500

600

700

800

Heat Treatment Temperature (C)

900

Transformation Temperature (C)

Transformation Temperature (C)

100

400

600

700

800

120

(c)

120

500

900

Heat Treatment Temperature (C)

(d)

100
80

Af

60

Rsh

As
Rsc
Rfc

40

Ms
20

Mf

0
400

500

600

700

800

900

Heat Treatment Temperature (C)

Figure 4. Transformation temperatures of (a) TMTCR10%, (b) TMTCR20%, (c) TMTCR30%, and (d)
TMTCR40%

In Fig. 4(a), for the 10% cold worked samples, as the final annealing temperature is
increased, Ms and Mf are found to increase gradually up to 600 C followed by a slight drop
up to 800 C. As and Af are found to decrease as the final annealing temperature is increased

Thermomechanical Treatments for Ni-Ti Alloys 9

from 400 to 500 C. Further increase up to 700 C shows gradual increase followed by a
decrease for the final annealing temperature of 800 C.
In Fig. 4(b), it is observed that for the 20% cold worked samples, there is R-phase formation
while cooling (Rsc, Rfc) and while heating (Rsh). As the final annealing temperature is
increased, Rsc and Rfc are found to increase till 500 C. For higher final annealing
temperatures, the R-phase formation is no longer detected. Ms and Mf increase with
increasing final annealing temperature until it reaches 600 C, followed by a slight decrease
when the sample is heat treated at 700 C. For the final annealing at 800 C, Ms is not
possible to be determined, but Mf increases slightly. As is found to increase with increasing
final annealing temperature up to 700 C along with Af. For the final annealing temperature
of 800 C, As was not possible to be determined and Af decreases. For this same treatment
(800 C), the R-phase formation is once again detected during cooling and heating.
In the case of samples 30% cold worked, as shown in Fig. 4(c); the R-phase is only present
during cooling for final annealing temperatures up to 500 C (Rsc and Rfc increase with
increasing final annealing temperature). Ms and Mf increase for increasing final annealing
temperature up to 600 C, slightly decrease for 700 C and then slightly increase for 800 C.
As and Af slightly decrease from 400 to 500 C and then increase and stabilize after 500 C.
In Fig. 4(d), it is observed that for the samples 40% cold worked and heat treatment there is
R-phase formation only during cooling for the final annealing temperature up to 500 C. (Rsc
and Rfc are found to increase with increasing annealing temperature). Ms and Mf increase
with increasing final annealing temperature till 600 C. For the final annealing temperature
of 800 C, Ms and As were not possible to be determined. For the final annealing temperature
of 800 C, the R-phase formation is once again detected.
The absence of the R-phase formation in the sample annealed at 500 C (not cold-rolled),
may be explained by the annealing out of the structural defects and generation of the strain
free crystals [19]. The same result is observed for the sample that has been cold-rolled to 10%
(very close to the maximum recoverable strain of this class of alloys). With increasing extent
of cold-work deformation, the R-phase deformation is only detectable for final annealing
temperatures below 500 C or at 800 C. The final annealing temperature above 500 C
induces a recrystallization of the marformed matrix that makes the single-step
transformation B2B19 more favorable [14, 20, 21]. This transformation may be initiated at
the coherent interfaces of the very narrow precipitates Ti2Ni. For the highest final annealing
temperature (800 C) the R-phase formation is once again present and this may be associated
to the coalescence of the Ti2Ni precipitates, making the B2 / Ti2Ni interfaces incoherent [22,
23]. When the DSC and ER results in Figs. 1 and 2 are compared, it is apt to mention that
when there is overlap of the phases transformation, ER technique is in a better position to
reveal the presence of distinct phases.
Table 1 summarizes the transformation sequences of the samples after the
thermomechanical treatments. For the samples cold worked to 10% and subsequently heat
treated up to 700 C, the transformation sequence is found to be clearly one-step (B19B2).
On the other hand, no matter the thickness reduction by cold-rolling, when the final

10 Shape Memory Alloys Processing, Characterization and Applications

annealing temperature is between 500 C and 700 C, the transformation is also clearly onestep (B19B2). The two-steps phase transformation while cooling is only observed for the
samples cold-rolled to 30 and 40% and for the final annealing temperatures of 400 C. The
multiple-steps phase transformation (with overlap) is only observed in two situations: (i) for
the final annealing temperature of 800 C, no matter the cold-work reduction, both while
cooling and heating, and (ii) for the samples cold-worked to 20 to 40%, where the final
annealing temperature was 500 C or below.
HTT (C)

Reduction by Cold Rolling

10%

20%

30%

40%

400

+/+

++ / +

++ /

450

+/+

500

+/+

+/+

+/+

+/+

600

+/+

+/+

+/+

+/+

700

+/+

+/+

+/+

+/+

800

On Cooling / On Heating: + one-step; ++ two-steps;

Multiple-steps with overlap; suspect multiple-steps with overlap.

Table 1. Influence of the thermomechanical processing (marforming) conditions on the transformations

sequence.

Deformation up to 10% thickness reduction decreases the shape memory effect capability.
This behavior is associated with the reorientation of martensite variants and increase of
dislocation density, giving rise to a stabilization of martensite at a higher temperature in
agreement with previous results [24].

4. Effect of cooling rate during heat treatments

During the heat treatments, one of the parameters which, can be easily controlled is the
cooling rate. Otsuka et al., adopted a heat-treatment in which they homogenized the
Ni50at%-Ti alloy for 1 h at 1000 C followed by furnace cooling to eliminate the vacancies
and the disorder to some extent. They found that quenched specimen has almost the same
transformation temperatures as the furnace cooled one [25]. It was found earlier by Saburi et
al., that during heat-treatment, Ms and mechanical behavior of Ni-rich off-stoichiometric
(>50.7at% Ni) NiTi alloys were sensitive to rate of cooling, whereas, of a near-stoichiometric
(50.4 at% Ni) alloys were not [26]. Sitepu et al., showed that precipitation of Ni4Ti3 particles
occurred in a matrix of Ni-rich Ni-Ti SMA of nominal composition Ni50.7at%-Ti, when it
was solution annealed at 850 C for 15 minutes followed by water quenching and aging at
400 C for 20 h [27]. In a more recent study, transformation behavior of NiTi alloys of
different composition, heat treated by employing quenching and furnace cooling were
investigated [28].

Thermomechanical Treatments for Ni-Ti Alloys 11

Electrical Resistivity (a.u.)

(a)

(b)

-200

-150

-100

-50

50

100

Temperature (C)
Figure 5. Electrical resistivity profiles for (a) Ni54.76wt%-Ti and (b) Ni56.00wt%-Ti alloys in the asreceived condition

Fig. 5 shows resistivity profiles for the 2 samples, (a) Ni54.76wt%-Ti, i.e. Ti-rich and
Ni56.00wt%-Ti, i.e. Ni-rich Ni-Ti alloys, in the as-received condition. For Ti-rich alloy, Rphase is found to occur only on cooling and the transformation is confined to a temperature
interval of about 60, above 0C. In the case of Ni-rich alloy, R-phase is found to appear both
while heating and cooling, and its temperature interval is spread over a wide temperature
range of more than 150, below +50C, and these materials do not undergo the
transformation to M-phase in the observed temperature range.
Fig. 6 (a-c) and 6 (d-f) show the resistivity profiles of the quenched and furnace cooled
samples of Ti-rich alloy, respectively. In both cases, profiles are similar. R-phase
transformation is only present during cooling for all the samples annealed between 100 and
420C and the transformation region decreases, with increase in annealing temperature due
to the increase in Ms temperature. For the annealing temperatures between 420- 800C, Rphase is found to be absent.
Fig. 7 (a-d) and 7 (e-h) demonstrate the resistivity profiles of the Ni-rich alloy for the
quenched and the furnace cooled samples respectively. For the quenched samples, annealed
in the temperature range of 100- 500C, two-stage transformation ARM during cooling
and MRA during heating are observed. When annealed between 500 and 600C, twostage transformation is observed only in cooling, with decrease in the temperature interval
of R-phase. Annealing above 600C, further suppression of R-phase takes place promoting
only MA transformation. In the case of furnace cooled alloy, with increase in annealing

12 Shape Memory Alloys Processing, Characterization and Applications

temperature, a unique discontinuous behavior is observed. With increase of annealing

temperature from 100 to 440C, two-stage transformation is observed both during cooling
and heating in the resistivity profile, with reduced R-phase temperature interval. Annealing
the sample between 440 and 580C, R-phase is found only on cooling with further
reduction in the temperature interval. For the sample annealed at 590C, a sudden increase
in the temperature interval of R-phase takes place. Hence, annealing around 590C seems to
be very critical. Annealing above 590C, two-stage transformation is seen both during
heating and cooling in the resistivity profile, regaining the initial behavior. The profiles
indicate the stabilization of various phases above annealing temperatures of 590C.
o

Electrical Resistivity (a.u.)

(a) Q100 C

(d) F100 C

(e) F420 C

(f) F800 C

(b) Q420 C

(c) Q800 C

-150 -100 -50

50 100

-150 -100 -50

50 100 150

Temperature ( C)
Figure 6. Resistivity profiles for the quenched and furnace cooled Ni54.76wt%-Ti alloys annealed at
different temperatures.

For lower annealing temperatures, all the samples of the two alloys, both quenched and
furnace cooled, exhibit similar behavior, i.e., Ms increases with increase in annealing
temperature, which is attributed to the release of energy stored during the cold work. Cold
work introduces high density of lattice defects, residual strain and internal stresses in the
materials, which hinders from the movement of martensite interfaces. On annealing such
cold worked materials, thermally activated diffusion leads to the annihilation of lattice
defects, promoting martensitic transformation [29]. For the quenched samples, at higher

Thermomechanical Treatments for Ni-Ti Alloys 13

annealing temperatures, this trend continues and gradual reduction in R-phase facilitates
MA transformation. But, the furnace cooled samples, after annealing at higher
temperatures, behave differently. A comparison of the resistivity profiles for the quenched
and furnace cooled samples, especially annealed at higher temperatures, indicates that Nirich alloy is sensitive to the cooling procedure, unlike Ti-rich alloy. There is not much
difference in the behavior of Ti-rich alloy either furnace cooled and quenched. In the case of
furnace cooled Ni-rich alloy a unique discontinuous behavior is observed, for annealing at
590 C. This may be due to the microstructural variations, arising as a consequence of two
competing processes, viz., annihilation of defects and precipitation. Annealing above this
critical temperature, the sample is able to regain and sustain a two-stage transformation,
which may be attributed to the dominance of precipitation process over the defect
annihilation process. It is proposed that, there is increased chance for Ti3Ni4 precipitation
while furnace cooling, due to the slow cooling process and the presence of the material at
higher temperature for a longer time. As reported by Nishida et al., Ti3Ni4 precipitates have
rhombohedral structure and are coherent to the matrix having a B2 type structure [30].
o

Electrical Resistivity (a.u.)

(a) Q100 C

(e) F100 C

(f) F500 C

(g) F590 C

(h) F800 C

(b) Q500 C

(c) Q590 C

(d) Q800 C

-150 -100 -50

50 100

-150 -100 -50

50 100

Temperature (C)
Figure 7. Resistivity profiles for the quenched and furnace cooled Ni56wt%-Ti alloys annealed at
different temperatures.

14 Shape Memory Alloys Processing, Characterization and Applications

5. Hot working
Both rolling temperature and thickness reduction are important factors that influence the
work hardening and hardness of hot-rolled plates. The greater the thickness reduction, the
greater the number of dislocations retained, and therefore, the greater the rate of work
hardening. At rolling temperatures 600 C, recovery or recrystallization occurs. However,
because of the short rolling time and the fast cooling in air, the recovery or recrystallization
is incomplete [31]. Hot-rolled Ni-Ti materials are found to possess enhanced resistance to
low-cycle fatigue (increased pseudoelastic stability) as long as the primary material
processing route remains unchanged [32]. Paula et al., recently studied Ni-Ti alloys
subjected to heat treatment at 767 C for 300 s followed by hot rolling (50%) after cooling in
air to 500 C and water quenching to room temperature (Troom). Phase transformations were
studied using differential scanning calorimetry, electrical resistivity measurements and in
situ X-ray diffraction [18].

(a)

B19'

Heat Flow (a.u.)

B2

B2

B19'

B19'

B19'

Electrical Resistivity (a.u.)

R
B19'

B2

(b)
B19'

B2

B2

B2
B19'
B19'

B2

20

40

B2

60

80

Temperature (C)
Figure 8. (a) DSC and (b) ER curves for TMTHR500 samples.

100

120

140

Thermomechanical Treatments for Ni-Ti Alloys 15

Fig. 8 (a & b) shows the DSC and ER curves for the ausformed at 500 C (TMTHR500)
samples. During the cooling and heating stages, multiple-step (B2R, B2B19, RB19)
phase transformation is clearly detected in both techniques. During heating, a small kink in
the DSC and a small hump in ER plots around 60 C show the presence of R-phase
associated to multiple-step, (B19R, B19B2, RB2), phase transformation. It was found
that the ausforming at 500 C promotes multiple-step phase transformation on cooling and
heating (B2R; B2B19; RB19). During the ausforming process at 500 C, it is not
achieved a full recrystallization, in agreement with other authors results [33]. Ausforming
introduce many defects in the sample, so that R-phase formation becomes necessary to
decrease the energy for B2B19 or B19B2 transformations.

6. Thermal cycling
Thermoelastic martensitic transformation appears to be very sensitive to thermal cycling [34,
35]. Also, thermal and mechanical treatments can suppress slip deformation resulting in
increase of flow stress and modify the transformation temperatures, recovery stresses and
recovery strains [36]. These observations indicate that the transformation process is strongly
affected by irreversible changes in the microscopic state of the alloy introduced by thermal
cycling. Thermal cycling causes a decrease in the characteristic temperatures and heats of
transformation [37]. Also, thermal cycling is found to promote the intermediate R-phase
transformation [38]. The effect of training conditions and extended thermal cycling on the twoway shape memory behavior of nitinol has been studied by Hebda and White, 1995 [39].
Thermal cycling under constant load was studied by de Araujo et al., 2000 [40] and they
concluded that the internal stresses created were effective in inducing two-way memory effect.
Below, in Fig. 9, phase transformations are studied during the ab initio 10 thermal cycles by
using DSC and ER techniques. In the DSC, thermal cycle was comprised of heating up to 140
C, holding for 360 s and subsequently cooling down to -30 C, with heating and cooling
rates being 7.5 K/min. ER characterization have been performed by making use of a home
made four-probe setup and the thermal cycling is performed by using the temperature
controlled silicone oil bath. Ni-Ti (Ti51at%-Ni) alloy has been previously subjected to a
series of thermomechanical treatment followed by heat treatment at 500 C for 30 min. [41].
In Fig. 9 (a & b), during the first thermal cycle, in both the techniques (DSC & ER), it is
observed that one-step phase transformation takes place. As the thermal cycling progresses,
phase transformation processes are found to shift toward lower temperatures, both while
heating and cooling. In Fig. 9(a), DSC thermograms for the first and second thermal cycles,
the phase transformation peaks are observed to be symmetrical both while heating and
cooling attributing to one-stage MA transformation. Also, in the ER profile shown in Fig.
9(b) corresponding to the first and second thermal cycles, it is observed that the specimen
undergo one-step MA transformation. As the number of thermal cycles is increased, DSC
thermogram peaks is found to broaden asymmetrically and shift toward lower temperatures
(from the fifth cycle onward), giving rise to increasing evidence of the intermediate R-phase
transformation while cooling (Fig. 9b).

16 Shape Memory Alloys Processing, Characterization and Applications

Figure 9. Evolution of phase transformation during thermal cycling up to 10 of the Ni-Ti specimens
subjected to series of thermomechanical treatment followed by heat treatment at 500 C for 30 min. (a)
DSC and (b) ER profiles.

This shows that the Ti-rich Ni-Ti alloy under study, when subjected to thermal cycling, after
multiple steps of thermomechanical treatments followed by final heat treatments, the
stability of the phase transformation is found to sensitive and depend on the final heattreatment temperatures. Further, the thermal cycling process also found to affect the nature
of phase transformation. Further, it can also be inferred that different thermomechanical
treatments applied on a specimen are found to have opposing effects on the nature of phase
transformations. In contrast to the heat treatments, which tend to increase the phase
transformation temperatures, thermal cycling tends to decrease them.

7. Severe plastic deformation

The plastic deformations carried out by cold-working and hot-working presented above
have been extended in the recent past, by subjecting these alloys to severe plastic
deformation (SPD). It was shown that the effects of high density of grain boundaries on the
martensitic phase transformation and the functional properties of SMA became a focus of
research investigating the impact of ultrafine and nanograins on the parameters of the SME
and SE. Further, methods of SPD, such as high pressure torsion (HPT) and equal channel
angular pressing (ECAP) have been successfully applied to achieve ultrafine grained (UFG)
and bulk nanostructured SMA [4245].
a.

High pressure torsion (HPT)

Waitz et al. [44] showed that martensitic transformation shifts to low temperature when the
grain size is less than 150 nm. Initially in their experiments, NiTi alloy was subjected to
HPT and later annealed close to recrystallization temperature. By post-deformation
annealing at 300C, it was found that the amorphous structure created by the roomtemperature HPT loses its thermomechanical stability and intensively crystallizes [45]. The
effect of the composition on the phase transformations in NiTi alloys subjected to HPT and
followed by heat treatments was recently reported [46].

Thermomechanical Treatments for Ni-Ti Alloys 17

Bulk Ni-Ti SMA with different compositions have been chosen and subjected to HPT and
their phase transformation characterization was carried out. The selected Ni(49.6 to
49.4at%)-Ti (Ti-rich) alloy in the as-received (AR) condition has Mf above RT and Ni(around
50.8at%)-Ti (Ni-rich) has Af below RT. SPD of Ni-Ti alloys (Ti-rich and Ni-rich) have been
performed by HPT at RT. Further, HPT processed separate specimens are subjected to heat
treatments at temperatures of 300C (HPT+HTT300) and 350 C (HPT+HTT350) for 20 min,
and quenched into water at room temperature. Phase transformation temperatures are
analyzed by studying the Differential Scanning Calorimeter (DSC) plots. Further, the
structural evolution of the samples subjected to SPD in the phase transformation
temperature region was studied using in situ X-ray diffraction (XRD) from 180 to +180C.
The phase transformation temperatures obtained from the thermogram plots of the
corresponding sample conditions are presented in Fig. 10. In Fig. 10a, for the Ti-rich alloy in
all the conditions, the transformation temperatures correspond to one-step MA phase
transformation both while heating and cooling. While compared to the transformation
temperatures of the AR sample, it is observed that, for the HPT sample, there is a slight
decrease in Mf and As temperatures, whereas Ms and Af temperatures increase. As a result,
both while heating and cooling, there is a broadening of the temperature intervals in which
the phase transformations take place. For the HPT sample after heat treatment at 300C,
designated as HPT+HTT300 in the plot, there is an increase in Mf and As temperatures,
whereas Ms and Af temperatures decrease. These results, both while heating and cooling, on
narrowing of the temperature intervals where the phase transformations are taking place.
After heat treatment at 350C, designated as HPT+HTT350 in the plot, all the transformation
temperatures increase and the phase transformation temperature intervals become
narrower.
In Fig. 10b, for the Ni-rich alloy in the AR and HPT conditions, the transformation
characteristics show a one-step MA phase transformation, both while heating and cooling.
It is observed that for the HPT sample, the temperatures corresponding to both phase
transformations are higher than those corresponding to the AR sample. However, both
while heating and cooling, corresponding to MA and AM transformations, respectively,
there is a narrowing of the transformation temperature intervals. For HPT+HTT300 sample,
Ms decreases, As, and Af increase considerably. Mf decreases to a value below the lower limit
of the scanned temperature range. The dashed lines represent the trend of the variation of
Mf. Further, R-phase transformations are present both while heating and cooling. On heat
treatment at 350C after the HPT processing, i.e., for Ni-rich HPT+HTT350, it is observed
that all the transformation temperatures tend to increase.
AR samples and samples subjected to HPT of both alloys are scanned using XRD technique
at different temperatures in the phase transformation temperature range. 3D view of the
XRD profiles obtained while cooling and heating are presented in Fig. 11. Miller indices of
the diffraction peaks emerging from the corresponding planes of the phases are marked on
each peak. In Fig. 11a, for the Ti-rich Ni-Ti AR sample, it might be observed that the
recording of the XRD pattern is started at 180C, where austenite phase exists, followed by

18 Shape Memory Alloys Processing, Characterization and Applications

cooling and recording the spectra at different temperatures until the martensite
transformation is complete, i.e., down to -40C. Further, the sample is again heated to
observe the transformation to austenite, i.e., up to 180C to complete the thermal cycle.
While cooling from 180C to -40C, the peak B2(1 1 0) corresponding to austenite (B2 cubic
structure) gradually disappears and peaks associated to martensite (B19 monoclinic
structure) gradually grow. The diffraction pattern obtained at -40C, shows the peaks
corresponding to martensite. As the temperature is increased from -40 to 180C, the peak
corresponding to (1 1 0) of austenite (B2 structure) gradually grows and the peaks
corresponding to B19 martensite gradually disappear. In Fig. 11b, for the Ti-rich Ni-Ti
sample subjected to HPT, also MA phase transformation behavior is observed.
Transformation temperatures (C

120

(a)

110
100
90

Af
As

80

Ms
Mf

70
60
50
40
AR

HPT

350
300
+HTT
+HTT
HPT
HPT
Ti-rich Ni-Ti conditions

Transformation temperatures (C)

60

(b)

40
20

Af
As

R'f
R's

-20

Rs
Rf

-40

Ms

-60

Mf

-80
-100
AR

HPT

+H
HPT

0
TT30

+H
HPT

0
TT35

Ni-rich Ni-Ti conditions

Figure 10. Phase transformation temperatures obtained from DSC plots of (a) Ti-rich and (b) Ni-rich
Ni-Ti alloys in different conditions.

Thermomechanical Treatments for Ni-Ti Alloys 19

Figure 11. 3-D box layout of the XRD profiles obtained during cooling and heating for Ti-rich Ni-Ti
alloy in (a) AR and (b) HPT conditions, and Ni-rich Ni-Ti alloy in (c) AR and (d) HPT conditions.

20 Shape Memory Alloys Processing, Characterization and Applications

Fig. 11c shows the phase transformation behavior of Ni-rich Ni-Ti alloy in the AR
condition. At 100C, the sample is found to be in austenite (B2) phase. As the temperature
is decreased down to -180C, the intensity of the peak corresponding to B2(1 1 0)
decreases. As the cooling progresses, the diffraction peaks corresponding to B19
martensite appear. On heating, the peaks related to B19 martensite disappear and the
peak related to B2(1 1 0) appears again. Similar phase transformation behavior is observed
for the Ni-rich sample after HPT (Fig. 11(d)). 3D layout of the XRD patterns obtained at
selected temperatures during cooling, followed by heating for both Ti-rich and Ni-rich NiTi alloys in HPT+HTT300C and HPT+HTT350C conditions were presented in a recent
publication [47]. It is clearly observed that the diffraction peaks corresponding to
intermediate R-phase are present for the Ti-rich and absent for the Ni-rich Ni-Ti alloys,
both while cooling and heating. The result is in agreement with the transformation
temperature profiles obtained by DSC thermogram analyses presented in the above
Fig. 10.
The results show that for Ti-rich Ni-Ti alloy, after HPT, as well as following the heat
treatments, there are no major changes in the phase transformation behavior. But, for Nirich Ni-Ti alloy, there is a slight change in the phase transformation behavior after HPT
process, and the final heat treatments bring about very significant change, namely, the
presence of intermediate R-phase transformation. In the present experiment, during the
HPT process, a high speed of rotation of the piston (1,250 rpm) is involved. Initially, when
the pressure torque is applied, a very intense and rapid plastic deformation takes place. This
causes the specimen to get macroscopically distorted geometrical shape and eventually
microscopic disorder. Owing to the process, the specimen gets heated up and might
undergo a short duration annealing in the severely strained condition before cooling to
room temperature. This situation may lead to accommodate several conflicting processes
[46]. High speed of rotation during the HPT process might also trigger dynamic
recrystallization. Depending on factors, such as the previous condition of the HPT
specimen, strain accommodated, temperature attained, and magnitude of the time
interval at which the specimen is at high temperature, different final microstructural
states will be achieved in the specimen. On one hand, the intense deformation will distort
the microstructure and long range order will be broken. On the other hand, the high
temperature will have its influence on the recovery of the strains and formation of strain
free submicrocrystals.
b.

Equal channel angular pressing (ECAP) or Equal channel angular Extrusion (ECAE)

ECAP is an attractive processing technique for several reasons. Processing by ECAP can
have a strong effect not only on the mechanical properties but also on the functional
properties of materials [48]. However, for Ni-Ti SMA, it is difficult to apply ECAP at RT due
to their low deformability and accordingly several reports have appeared describing the
fabrication of ultrafine-grained alloys using ECAP at elevated temperatures [49]. The
transformation behavior of TiNi alloy after ECAE process has been reported by Zhenhua Li

Thermomechanical Treatments for Ni-Ti Alloys 21

et al., [50] by using the experimental material, Ti-50.6at% Ni alloy rods, with a 25 mm
diameter, after 850 C hot forging and 500 C annealing for 2 h. They concluded that during
high temperature ECAE process, there was no dynamical re-crystallization but, most
probably, there was dynamical recovery. Annealed for 5 min at 750 C after two passes of
ECAE, grains were refined and became even. After two passes of ECAE, transformation
temperatures of the billet of TiNi alloy sharply decreased. Transformation temperature of
the sample remarkably increased annealed for 2 h at 500 C after two ECAE processes,
similar to the one of TiNi alloy before ECAE process, which was related to Ni content in the
matrix.
Effect of ECAP process on the microstructure and functional properties, such as recovery
stress and maximum fully recoverable strain has been reported. The results show that the
multipass ECAP of Ni50.2Ti49.8 alloy allows one to produce a uniform grain structure with
predominantly high-angle grain boundaries with a grain size of about 200-300 nm. ECAP
increases strength and insignificantly decreases plasticity as compared to the as-quenched
state. The strength increases more than 50% with increasing number of passes; after ECAP
using 12 passes. The functional properties of the Ni50.2Ti49.8 alloy after ECAP are
substantially improved. With increasing number of ECAP passes the maximum recovery
stress rises to 1100 MPa and the degree of maximum fully recoverable strain increases to
9.2% [51].

8. Concluding remarks
Phase transformations can be studied by using various characterization techniques, such as
DSC, ER, Internal Friction (IF), dilatometry, XRD, and optical/electron microscopy [5, 14, 1619, 41, 43, 52, 53]. Each of these techniques senses different physical phenomena and thus
provides information concerning the changes of various physical parameters taking place
during the phase transformations. Because of their distinctive nature, when these techniques
are employed individually, only partial information about the phase transformation can be
delivered.
DSC measures only the sum of all thermal events and, as a result, some important features
may be ignored or the results are easily misinterpreted in the cases involving weak and/or
complex (overlapping) transformations [5, 16, 18, 19]. ER is the structural sensitive
property of a material and it reveals changes during crystallographic phase
transformations. In fact, it is found to be more sensitive than DSC in detecting the phase
transformations which occur in a narrow temperature range [19, 41]. Dilatometry is
capable of sensing small volume changes during phase transformations. Only a limited
number of publications report the use of dilatometry to study the phase transformations
in Ni-Ti shape memory alloys [17, 19]. These methods have been widely accepted to detect
the phase transformations in Ni-Ti SMAs. A combined approach of several
characterization techniques would lead to the proper understanding of the phase
transformations involved.

22 Shape Memory Alloys Processing, Characterization and Applications

Author details
F.M. Braz Fernandes* and K.K. Mahesh
CENIMAT/I3N, Departamento de Cincias dos Materiais, FCT/UNL, 2829-516 Caparica,
Portugal
Andersan dos Santos Paula
Post-graduated Program in Metallurgical Engineering, UFF - Universidade Federal Fluminense,
Volta Redonda, Brazil

Acknowledgement
The pluriannual financial support (by Fundao para a Cincia e a Tecnologia Ministrio
da Educao e Cincia) of CENIMAT/I3N through the Strategic Project - LA 25 - 2011-2012
and the research project Smart Composites (PTDC/CTM/66380/2006) is gratefully
acknowledged by KKM and FMBF. KKM gratefully acknowledges the fellowship under the
scheme, Cincia 2007 with Ref. No. C2007-443-CENIMAT-6/Cincia2007.

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